CN1133687C - Polysilazane with line-ring structure and its preparation method - Google Patents
Polysilazane with line-ring structure and its preparation method Download PDFInfo
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- CN1133687C CN1133687C CNB991239865A CN99123986A CN1133687C CN 1133687 C CN1133687 C CN 1133687C CN B991239865 A CNB991239865 A CN B991239865A CN 99123986 A CN99123986 A CN 99123986A CN 1133687 C CN1133687 C CN 1133687C
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Abstract
The present invention relates to polysilazanes in a linear-cyclical structure. The general chemical formula of the polysilazanes is disclosed in the specification. The polysilazanes has a structural formula as the formula on the right side, wherein R and R<1> represent an alkyl group and a phenyl group, the alkyl group and the phenyl group respectively contain 1 to 6 C atoms, and R and R<1> can be identical or different; R<2>, R<3>, R<4> and R<5> representing a methyl group, a phenyl group, a vinyl group or H can be identical or different; x is equal to 0 or 1 (disclosed in the formula), m is an integer of 1 to 20, a is H or a unit (disclosed in the formula), and H and the unit can be identical or different, and n is an integer of 1 to 5. The polysilazanes is prepared from lithium salt of cyclosilazane and alpha, omega-dichlorosilazane as reaction raw materials reacting at the reaction temperature of-30 to 70DEG C, and the reaction time is from 0.5 to 24 hours.
Description
The present invention relates to a kind of polysilazane and preparation method thereof.
Can form the Si-N key by nitrogen lithium salts and chlorosilane reaction, be an effective way of synthesizing new silazane.U.S.Patent4, in 482,669 by alkyl hydrogen dichlorosilane ammonia hydrolysis products through the KH catalyzed polymerization, prepared the polysilazane that ring links to each other with ring structure, must contain ≡ SiH-NH-structural unit but this method is raw materials used, the monomer source is restricted; Patent U.S.Patent5 by the silazane that contains the N-H key successively and lithium alkylide, chlorosilane reaction, obtains containing the silicon-nitrogen polymer of reactive functional groups, but does not contain the ring silazane structure in 086,126; Document Orgametallics, 1989,8:1980 has reported that causing the ring-opening polymerization of ring disilazane by lithium alkylide prepares high molecular line style polysilazane, but above-mentioned document does not all relate to the polysilazane of line-ring structure.
The present invention provides a kind of polysilazane of line-ring structure on the prior art basis.Polysilazane with line-ring structure general formula of the present invention is:
Wherein, R, R
1Represent alkyl, the phenyl of 1～6 C atom, can be identical or different
R
2, R
3, R
4, R
5, represent alkyl, phenyl, vinyl or the H of 1～6 C atom, but phase
Same or different
X=0 or 1
M is 1～20 integer or non-integer
A is H or unit
Can be identical or different
N is 1～5 integer
Polysilazane of the present invention step in the following order is prepared: 1, the lithium salts of preparation ring silazane
To encircle silazane and n-Butyl Lithium and be in molar ratio 1: 1～1: 4 at N
2Under the gas shiled, stir in organic solvent and react, after reaction finished, removal of solvent under reduced pressure was then in N
2Under the gas shiled,, be neutral until elutant with normal hexane thorough washing lithium salts.Through removal of solvent under reduced pressure, obtain the nitrogen lithium salts.According to ring silazane and different with the n-Butyl Lithium reaction ratio thereof, can obtain a lithium salts, dilithium salt, three lithium salts and four lithium salts.Temperature of reaction is-60～30 ℃, and solvent for use comprises aromatic hydrocarbon, tetrahydrofuran (THF), ether of the alkane of 6～12 C atoms, 6～9 C atoms etc.2, synthetic polysilazane
By ring silazane lithium salts and the α that step 1 obtains, ω-dichloro silazane carries out the solution condensation polyreaction.Ring silazane lithium salts and α, the mol ratio of ω-dichloro silazane is 1: 0.5～1: 4, and temperature of reaction is-30～70 ℃, and the reaction times is 0.5～24 hour.Used solvent comprises alkane, tetrahydrofuran (THF) or their mixing solutions of 6～12 C atoms.3, the processing of polysilazane
After step 2 reaction finishes, under 25 ℃ of stirrings, in above-mentioned mixing solutions, lead to NH
33～10 hours, then at N
2Protection removes by filter the LiCl precipitation down, and filtrate is removal of solvent under reduced pressure again, obtains polymkeric substance; If with the tetrahydrofuran (THF) is solvent, then tetrahydrofuran (THF) is removed in decompression earlier, adds a certain amount of n-hexane dissolution polymkeric substance again, removes by filter LiCl then, obtains polymkeric substance after filtrate decompression desolventizes.
The line style polysilazane is inclined to into ring, is not suitable for being used as ceramic forerunner; The polysilazane that ring links to each other with ring structure has particular requirement to reaction raw materials, must contain ≡ SiH-NH-structural unit, and the monomer source is restricted.Present method has overcome the defective of prior art, and a kind of polysilazane of line-ring structure is provided, and can be used for the Si-C-N ceramic forerunner.
Embodiment 1:
In there-necked flask, N
2Protection down adds pregnancy basic ring three silazane lithium salts 4.0g, and 1,3-two chloro-1,1,3,3-tetraphenyl disilazane 4.0g, tetrahydrofuran (THF) 30ml, 70 ℃ of stirring reactions 2 hours.Again in 25 ℃ of logical NH
3And stirred 3 hours.After tetrahydrofuran (THF) is removed in decompression, add normal hexane 80ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance, consists of C
36N
7H
61Si
8, structural formula is
Results of elemental analyses (%): actual measurement N12.46, C53.18, H7.46; Theoretical N12.02, C53.01, H7.48.
29Si NMR: δ=-3.6 (Si (CH
3)
2), δ=-22.3 (Si (C
6H
5)
2), molecular weight: VPO surveys M
n=830, theoretical M
n=815.
Embodiment 2:
In there-necked flask, N
2Protection down adds pregnancy basic ring three silazane lithium salts 4.90g, and 1,3-two chloro-1,1,3,3-tetraphenyl disilazane 8.11g, tetrahydrofuran (THF) 60ml, 25 ℃ of stirring reactions 12 hours, logical again NH
3And stirred 3 hours.After tetrahydrofuran (THF) is removed in decompression, add normal hexane 80ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance, M
n=2167. structural formulas are
Embodiment 3:
In there-necked flask, N
2Protection adds pregnancy basic ring three silazane lithium salts 6.45g down, and 1,3-two chloro-1,1,3,3-tetraphenyl disilazane 6.50g, tetrahydrofuran (THF) 20ml, normal hexane 20ml, 0 ℃ was reacted 20 hours.25 ℃ of logical NH
3And stirred 3 hours.After the removal of solvent under reduced pressure, add normal hexane 75ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance, and structural formula is with embodiment 2.
Embodiment 4:
In there-necked flask, N
2Protection adds hexaphenyl ring three silazane lithium salts 3.67g down, and 1,3-two chloro-1,1,3,3-tetramethyl-disilazane 1.23g, tetrahydrofuran (THF) 20mi, normal hexane 40ml, 25 ℃ were reacted 0.5 hour, logical again NH
3And stirred 3 hours.After the removal of solvent under reduced pressure, add normal hexane 100ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance.Structural formula is
Embodiment 5:
In there-necked flask, N
2Protection adds pregnancy basic ring three silazane lithium salts 5.14g down, and 1,3-two chloro-1,1,3,3-tetraphenyl disilazane 5.03g, tetrahydrofuran (THF) 35ml ,-30 ℃ were reacted 24 hours.Again in 25 ℃ of logical NH
3And stirred 3 hours.After the removal of solvent under reduced pressure, add normal hexane 80ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance.Structural formula is
Embodiment 6:
In there-necked flask, N
2Protection adds prestox cyclotetrasilazane lithium salts 2.90g down, and 1,3-two chloro-1,1,3,3-tetraphenyl disilazane 4.29g, tetrahydrofuran (THF) 50ml, 25 ℃ of stirring reactions led to NH after 12 hours
3And stirred 3 hours.After tetrahydrofuran (THF) is removed in decompression, add normal hexane 100ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance.Structural formula is
Embodiment 7:
In there-necked flask, N
2Protection adds hexaphenyl ring three silazane lithium salts 3.01g down, and 1,3-two chloro-1,3-dimethyl disilazane 1.18g, tetrahydrofuran (THF) 30ml ,-30 ℃ were reacted 10 hours, again in 25 ℃ of logical NH
3And stirred 5 hours.After the removal of solvent under reduced pressure, add normal hexane 50ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance.Structural formula is
Embodiment 8:
In there-necked flask, N
2Protection adds prestox cyclotetrasilazane lithium salts 2.92g down, and 1,3-two chloro-1,3-divinyl disilazane 1.96g, tetrahydrofuran (THF) 10mi, normal hexane 30ml, 0 ℃ was reacted 10 hours, again in 25 ℃ of logical NH
3And stirred 10 hours.After the removal of solvent under reduced pressure, add normal hexane 60ml dissolve polymer.N then
2Remove by filter insoluble LiCl precipitation under the protection, filtrate decompression is removed and is desolvated, and obtains polymkeric substance.Structural formula is
Claims (10)
1, a kind of polysilazane with line-ring structure is characterized in that having following structure
Wherein, R, R
1Represent alkyl, the phenyl of 1～6 C atom, can be identical or different,
R
2, R
3, R
4, R
5Represent alkyl, phenyl, vinyl or the H of 1～6 C atom, but phase
It is same or different,
X=0 or 1,
M is 1～20 integer or non-integer,
A be H or
Can be identical or different,
N is 1～5 integer.
2, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
3, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
4, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
5, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
6, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
7, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
8, a kind of polysilazane with line-ring structure according to claim 1 is characterized in that described polysilazane with line-ring structure structural formula is:
9, the preparation method of a kind of polysilazane with line-ring structure according to claim 1 is characterized in that in the following order, step is prepared.
(1) presses 1: 1～1: 4 mol ratio in N by ring silazane and n-Butyl Lithium
2Under the gas shiled, prepared in reaction ring silazane lithium salts in hexane, tetrahydrofuran (THF) or their mixing solutions,
(2) ring silazane lithium salts and the α that obtains by step (1), ω-dichloro silazane be in molar ratio 1: 0.5～1: 4 in hexane, tetrahydrofuran (THF) or their mixing solutions in-30～70 ℃ the reaction 0.5～24 hour,
(3) after step (2) reaction finishes, 25 ℃ of logical NH
3Stirred 3～10 hours, then at N
2Protection removes by filter the LiCl precipitation down, obtains a kind of polysilazane with line-ring structure.
10, the preparation method of a kind of polysilazane with line-ring structure according to claim 9 is characterized in that hexane and tetrahydrofuran (THF) ratio are 0: 1～10: 1 in the described mixing solutions.
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| CNB991239865A CN1133687C (en) | 1999-11-23 | 1999-11-23 | Polysilazane with line-ring structure and its preparation method |
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|---|---|---|---|
| CNB991239865A CN1133687C (en) | 1999-11-23 | 1999-11-23 | Polysilazane with line-ring structure and its preparation method |
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|---|---|
| CN1303880A CN1303880A (en) | 2001-07-18 |
| CN1133687C true CN1133687C (en) | 2004-01-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435810B (en) * | 2013-07-15 | 2016-01-20 | 江苏大学 | A kind of preparation method of high temperature-resistanthermoplastic thermoplastic organic polysilazane |
| CN109485853B (en) * | 2017-09-11 | 2020-09-08 | 中国科学院化学研究所 | Polysiloxane/perhydropolysilazane hybrid polymer and synthetic method thereof |
| CN111303433B (en) * | 2020-03-04 | 2022-03-22 | 浙江理工大学 | Polysilazane with excellent spinning performance, preparation method thereof and melt spinning |
| CN114456389B (en) * | 2022-01-26 | 2023-04-28 | 江西信达航科新材料科技有限公司 | Modified organic polysilazane and preparation method thereof |
| CN114561016B (en) * | 2022-03-14 | 2022-12-30 | 江西信达航科新材料科技有限公司 | Benzenepyridazoline and preparation method thereof |
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